Polycyano-2, 5-dihydrofurans and their preparation



United States Patent Ofiicc 3,235,565 POLYCYANO-LS-DIHYDROFURANS AND THEIR PREPARATION William J. Linn, Wilmington, DeL, assignor to E. I. du

Pont de Nernours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Sept. 28, 1962, Ser. No. 227,069 Claims. (Cl. 260-3461) This invention relates to new heterocyclic compounds having a plurality of cyano substituents attached directly to the heterocyclic ring. More particularly, it relates to polycyano-2,5-dihydrofurans and a method for their preparation.

2,5-dihydrofurans are obtainable by oxide-forming ring closures of 2-butene-l,4-diols o1- -halohydrins, or from tetrahydrofurans in which a double bond in the 3,4-position can be formed by standard methods. However, appropriate intermediates to polycyanodihydrofur-ans by such routes are unavailable or are obtained with ditficulty.

The polycyano-2,S-dihydofurans of this invention are compounds having an unsaturated ring of 5 atoms consisting of 4 carbons and one oxygen and having at least one cyano group attached to each carbon adjacent to the oxygen, i.e., in the 2 and 5 positions, together with at least one additional substituent attached to a carbon adjacent to the oxygen, the unsaturation consisting of a double bond between the other two carbons, i.e., between the 3 and 4 positions.

The compounds of this class can be represented by the formula (I) A o B NC O \OZC D-=CE in which A is hydrogen, cyano, R, COOR, R or C H X, where R is an alkyl radical of from 1 to 18 carbon atoms, R; is polyfiuoro R, and X is in the para position and is hydrogen, halogen, nitro, R or OR; B is cyano, COOR or R D contains up to 12 carbons and is hydrogen, R (R being hydrocarbyl free of aliphatic carbon-carbon double bonds, i.e., hydrocarbyl in which any double bonds are in an aromatic ring), halo R in which all halogens are of atomic number 935 (i.e., fluorine, chlorine and/ or bromine), CH OR, C(O)OR, CI-I OC(O)R", -alkylene-C(O)OR (R being aliphatically saturated hydrocarbyl, i.e., any unsaturation is aromatic), dialkoxymethyl, or polyfluoroalkylthio; and E is D (i.e., E is one of the groups within the definition of D but is not necessarily identical to the particular D group), halogen of atomic number 1735 (chlorine or bromine), cyano or Where Q is hydrogen, R" or halo R, and Q is alkylene or haloalkylene in which all halogens are of atomic number 935, the total number of carbons in Q plus Q being up to 10.

The term hydrocarbyl in the above definition is used in the usual sense to denote the monovalent radical obtained by removal of one hydrogen from a hydrocarbon. In the present case the su-bstituents A, B, D and E are monovalent. Examples of hydrocarbyl radicals which can be present as D or E are alkyl, aryl, cycloalkyl, alkynyl, aralkyl, alkaryl, arcycloalkyl, cycloalkylaryl, alkcycloalkyl, cycloalkylalkyl and aralkynyl of up to 12 carbons.

The preferred compounds of Formula I are those wherein D is hydrogen, R (R"' being hydrocarbyl of up to 12 carbons which is free of aliphatic carbon-carbon double bonds and in which any aromatic unsaturation is conju- 3,235,565 Patented Feb. 15, 1966 gated with a triple bond), halo R' in which all halogens are of atomic number 9-35, CH OR, -C(O)OR", CH OC(O)R", -alkylene-C(O)OR" of up to 9 carbons, R" containing up to 7 carbons and otherwise being as defined above, CH[O(CH H] or -S-polyfiuoro loweralkyl (lower meaning 1 through 7 carbons); and E is D, halogen of atomic number 17-35, cyano or a moiety of Formula II wherein Q is hydrogen and Q is lower alkylene, i.e., (CH Generally D and E will contain a combined total of up to 18 carbons; however, this is not essential or critical in any respect.

Especially preferred, because their precursors are more readily available, are the dihydrofurans of Formula I wherein A and B are cyano, and also those wherein D and E together contain at most one acetylenic bond, or no acetylenic bonds in the event E is a moiety of Formula II.

The new compounds of this invention are obtained by reacting a polycyanoethylene oxide of the formula (III) A 0 B Q NO/ CN with an acetylenic compound of the formula (IV) DCECE' at a temperature of at least 75 C. The substituents A, B and D are as defined above in connection with Formula I, and E is D as defined above, halogen of atomic number 1735 or cyano. Preferably any aromatic unsaturation which is present in the acetylenic reactant is conjugated with an acetylenic bond.

The reaction time is not critical and will ordinarily vary from about 1 hour to several days, depending upon the specific temperature and pressure that are employed, longer times being needed to obtain substantially complete reaction at lower temperatures and pressures.

A reaction medium is unnecessary but can be used to advantage; and the medium can be an excess of the acetylenic reactant, a nonreactive solvent, such as 1,2- dichloroethane, or a potentially reactive solvent that is less reactive with polycyanoethylene oxides than the chosen acetylenic reactant, e.g., toluene can be used as a solvent in the reaction of tetracyanoethylene oxide with dimethyl acetylenedicarboxylate.

The proportions of polycyanoethylene oxide and acetylenic reactant are not critical and a stoichiometric excess of either can be used. Although a polycyanoethyl-v ene oxide normally can react with a compound having a carbon-carbon double bond in a manner similar to that of its reaction with an acetylenic compound, the intracyclic double bond in a polycyano-Z,S-dihydrofurau derived from a polycyanoethylene oxide and an acetylenic compound is not susceptible to further reaction with the oxide. Generally speaking, it is uneconomical to use a large stoichiometric excess of either the epoxide or the acetylenic reactant.

Polycyaoethylene oxides of the foregoing description can be obtained by procedures described in the copending, coassigned application Ser. No. 71,391, filed Nov. 25, 1961. Among these polycyanoethylene oxides, tetracyanoethylene oxide is especially preferred for the preparation of polycyano2,5-dihydrofurans because the olefin from which the oxide is prepared i.e., tetracyanoethylene, is available commercially and is therefore more accessible than other polycyanoolefins. Because of their greater accessibility, R groups containing up to 13 carbons each are preferred in epoxide starting materials having such substituents.

The reaction takes place readily at temperatures above about C., preferably at a temperature in the range of about C. to about 250 C.

The reaction pressure is not a critical factor and can be in the range of less than to greater than atmospheric pressure. Accordingly, reaction is accomplished in a reaction vessel suited to the chosen mode of operation. Although it is advantageous to carry out the reaction in a closed vessel under a pressure which may or may not be the autogenous pressure of the reactants, a reactor which is not closed pressurewise against the atmosphere can also be used. However, it is important to prevent escape of any reactant from the sphere of reaction whether in a closed or open vessel. When the vessel is otherwise open to the atmosphere, the reactants are confined by any suitable means such as a solvent and/or reflux condenser.

In an acetylenic compound which also contains aromatic carbon-carbon double bonds, the acetylenic bond or bonds will react preferentially with the polycyanoethylene oxide. If the aromatic double bonds are conjugated with a triple bond, they will not react in any event; but if such double bonds are not conjugated with a triple bond, one double bond of the aromatic ring can react with the polycyanoethylene oxide reactant to form a tetrahydrofuran ring if a stoichometric excess of polycyanoethylene oxide over that required to react with all reactive acetylem'c bonds is employed. (The reactive acetylenic bonds are defined in the next-succeeding paragraph.) Thus to avoid the possibility of reaction at sites of aromatic unsaturation which are not conjugated with a triple bond, the polycyanoethylene oxide should not be employed in substantial excess of that required to react with the reactive triple bonds. Although substantial reaction at reactive aromatic bonds is avoided when the mole ratio of polycyanoethylene oxide to reactive acetylenic bond is as [high as 1.511 (i.e., the majority of the product will not contain any tetrahydrofuran rings), it is preferred that this ratio be about 1:1.

If the acetylenic reactant has more than one acetylenic bond, and the bonds are conjugated, normally only one of these bonds will react even in the presence of excess polycyanoethylene oxide. Moreover, usually only one of two unconjugated acetylenic bonds in close proximity will react with one equivalent of the epoxide, though both will react if the epoxide is present in excess of one equivalent. On the other hand, if multiple unconjugated acetylenic bonds are widely spaced, the bonds will, in general, react simultaneously with separate epoxide molecules.

The term conjugated as used in this application refers to the relationship between sites of unsaturation exhibited by groups such as CEC-CEC,

CEC-phenyl and C C-phenylene-CEC. It is to be noted that in any series of conjugated unsaturation, the last bond of the series is considered as being conjugated not only with the next-adjacent bond, but also with the first bond of the series, e.g., in the group -CEC-phenyl, each double bond of the phenyl ring is conjugated with the depicted triple bond.

The polycyano-Z,S-dihydrofurans of the invention are usually crystalline solids which can be isolated and purified by well-known methods, e.g., filtration recrystallization from a solvent, or crystallization by sublimation.

As was noted above, the polycyanoethylene oxide precursors of the products of this invention are prepared by the method described in application Ser. No. 71,391. This method comprises reacting a compound of the formula \C=C/ NC/ \GN wherein A and B are as defined above, with aqueous hydrogen peroxide (at least 3% H by weight, conveniently 30% by weight) in solution in a single phase, preferably at a temperature of 20 C. to +50 C. and a pH of 68. The solvent used to prepare the single phase solution of reactants is a water miscible, inert organic liquid such as acetonitrile. A typical preparation is as follows:

A solution of 256 parts (by weight) of tetracyanoethylene in 1180 parts of acetonitrile is cooled at 0 C. and 344 parts of 30% hydrogen peroxide is added all at once. A transient violet color appears which soon fades to yellow. The solution is stirred for five minutes and diluted with 10,000 parts of ice water. The oil which separates soon solidifies and is collected by filtration and dried to give 200 parts (70% yield) of colorless crystals of tetracyanoethylene oxide. After recrystallization from ethylene dichloride, the product melts at 177178 C.

The invention is illustrated in greater detail in the fol lowing examples in which quantities of reactants (parts) are in terms of weight:

EXAMPLE I A. A mixture of 15 parts of tetracyanoethylene oxide, 10 parts of acetylene, and 188 parts of 1,2-dichloroethane was sealed in a pressure vessel and heated for 10 hours at C. The reaction mixture was filtered, and volatiles in the filtrate were evaporated. The residual solid was recrystallized from 1,2-dichloroethane to give 5.3 parts (30%) of colorless plates of 2,2,5,5-tetracyano-2,S-dihydrofuran, M.P. 159-160.5 C. The product melted at 160-161 C. after further recrystallization.

Analysis for C H N OCalcd.: C, 56.5; H, 1.2; N, 32.9. Found: C, 56.7; H, 1.2; N, 32.5, 32.5.

The product was further characterized by its infrared and nuclear magnetic resonance spectra.

B. A mixture of 25 parts of tetracyanoethylene oxide, 15 parts of acetylene, and 188 parts of 1,2-dichloroethane was heated in a sealed vessel for 16 hours at 130 C. The recovered reaction mixture was filtered to give 17.7 parts of crystalline product. An additional 9.7 parts of product was obtained by evaporated concentration of the filtrate. The two portions were combined and recrystallized from 1,2-dichloroethane to give 20.4 parts (71%) of 2,2,5,5- tetracyano-2,S-dihydrofuran, M.P. 159-161 C.

EXAMPLE II HCEGH (N (DEC A mixture of 15 parts of tetracyanoethylene oxide, 16 parts of 2-butyne and 188 parts of 1,2-dichloroethane was heated in a pressure vessel for 10 hours at 130 C. The reaction mixture was filtered, and volatiles in the filtrate were evaporated. The residual solid was dissolved in ethyl acetate, and the solution was boiled with charcoal and filtered. The resultant filtrate was diluted with an equal volume of cyelohexane and cooled. In this manner there was obtained 8.8 parts (43%) of pale tan crystals of 3,4-dimethyl-2,2,5,5-tetracyano-2,5 dihydrofuran, M.P. 128132 C. The melting point was raised to 134-135 C. by recrystallization of the product from a 50-50 mixture of benzene-hexane.

Analysis for C H N OCalcd.: C, 60.6; H, 3.0; N,

28.3. Found: c, 60.7; H, 3.1; N, 27.9.

EXAMPLE 111 O HGECCH3+ (NC)2C C(CN)g (NC) O C(CN)g were evaporated, to leave a pale brown solid which was recrystallied from 1/3 hexane/benzene. There was obtained 11.9 parts (60%) of tan plates of 3-methyl-2,2,5,5- tetracyano-2,5-dihydrofuran, M.P. 119l21 C. An analytical sample, purified by sublimation, melted at 120- 121 C.

Analysis for C H N OCalcd.: C, 58.7; H, 2.2; N, 30.4. Found: C, 58.9; H, 2.4; N, 30.2.

EXAMPLE IV 110zooGH,+ No 2o o cm, Nono owmz A mixture of 5.0 parts of tetracyanoethylene oxide, 3.6 parts of phenylacetylene and 63 parts of 1,2-dichloroethane was heated to reflux for 22 hours. The reaction mixture was cooled to room temperature and filtered. In this manner there was recovered 2.3 parts of tetracyano ethylene oxide, identified by means of its infrared spectrum. The filtrate was concentrated by evaporation to leave a solid residue, from which as much sublimate as possible was removed at 8090 C./0.1 mm. Additional sublimate was removed at 130 C./0.05 mm., and this latter fraction was recrystallized from benzene to give 1.07 parts (23%) of colorless crystals of 3-phenyl-2,2,5,5- tetracyano-Z,S-dihydrofuran, M.P. 136-137 C.

Analysis for C I-I N OCalcd.: C, 68.3; H, 2.5; N, 22.8. Found: C, 68.1; H, 2.7; N, 22.8.

EXAMPLE V O5H5CECC6H5+ (NCMCQCKJNM (NC)2C/ C(CN)z 0 11 0: CaHs A mixture of 5.0 parts of tetracyanoethylene oxide and 3.1 parts of diphenylacetylene in 109 parts of 1,2-dibromoethane was heated to reflux for 17 hours. The reaction mixture was cooled and filtered to give 1.14 parts of recovered tetracyanoethylene oxide, identified by means of its infrared spectrum. The filtrate was concentrated by evaporation, and the residue was washed with benzene to give 4.07 parts of pale gray crystals which were recrystallized from benzene to give 2.93 parts (53%) of colorless crystals of 3,4-diphenyl-2,2,5,5-tetracyano-2,5 dihydrofuran, M.P. 183184.5 C.

Analysis for C H N OCalcd.: C, 74.5; H, 3.1; N, 17.4. Found: C, 74.6; H, 3.2; N, 17.3.

EXAMPLE VII A suspension of 5.0 parts of tetracyanoethylene oxide and 2.71 parts of 2,4-hexadiyne in 84 parts of l-chloro-Z- bromoethane was heated to reflux for 17 hours. The reaction mixture was evaporated to leave 6.92 parts of dark solid, which was recrystallized from cyclohexane to give 5.25 parts of light tan crystals, M.P. -97 C. Further recrystallization of the product from cyclohexane raised the melting point to 9697 C. This was a mono-adduct of tetracyanoethylene oxide and 2,4-hexadiyne, as shown by the analysis and by the proton magnetic resonance spectrum. The product is identified as 2,2,5,5-tetracyano- 3-methyl-4-( l-propynyl) -2,5-dihydrofuran.

Analysis for C H N OCalcd.: C, 64.8; H, 2.72; N, 25.2. Found: C, 64.6; H, 2.98; N, 25.4, 25.3.

This example demonstrates the reaction of tetracyanoethylene oxide with a diacetylenic compound in which the acetylenic bonds are conjugated. Thus, reaction with 2,4- hexadiyne was confined substantially to only one of the acetylenic groups when the epoxide to hexadiyne mole ratio was 1:1 (i.e., one epoxide group to two acetylenic groups EXAMPLE VIII A suspension of 5.0 parts of tetracyanoethylene oxide and 1.56 parts of 1,6-heptadiyne in 84 parts of l-chloro- 2-bromoethane was heated to reflux for 21 hours. At the end of this time the reaction mixture was filtered to remove the insoluble precipitate consisting of 4.4 parts of tan needles, which were recrystallized from dioxane to give 3.0 parts of an adduct of 2 moles of tetracyano ethylene oxide and 1 mole of 1,6-heptadiyne that melted at 258 C. The product is identified as 3,3'-trimethylenebis(2,2,5,5-tetracyano-2,S-dihydrofuran).

Analysis for C H N O Calcd.: C, 60.0; H, 2.12; N, 29.5. Found: C, 60.9, 60.8; H, 2.39, 2.32; N, 29.4, 29.6. This example demonstrates the reaction of tetracyanoethylene oxide with a diacetylenic compound in which the acetylenic bonds are unconjugated. Thus, reaction with 1,6-heptadiyne occurred in substantial degree at both acetylenic bonds when the epoxide to heptadiyne mole ratio was large (i.e., one epoxide group to one acetylenic group). Similarly, reaction will occur at both actylenic bonds in 1,4-pentadiyne and 1,10-dodecadiyne if the latter are substituted for 1,6-heptadiyne in the process of this example.

EXAMPLE IX nczowumozon (NO)ZOL\C(CN)Z (NC)20/ \C(CN)2 H :owmnczort A suspension of 5.0 parts of tetracyanoethylene oxide and 9.4 parts of 1,6-heptadiyne in 84 parts of l-chloro- 2-bromoethane was heated to reflux for 17 hours. The reaction mixture was cooled to room temperature and filtered. There was recovered 0.54 part of the bis-adduct of tetracyanoethylene oxide and 1,6-heptadiyne. Evaporation of the filtrate left a viscous oil, which soon solidified and was recrystallized from a mixture of ether and petroleum ether to give 4.17 parts (51%) of the monoadduct of tetracyanoethylene oxide and 1,6-heptadiyne. The product melted at 7374 C. after further recrystallization from isopropyl alcohol, and it is identified as 2,2,5,5-tetracyano-3-(4-pentynyl)-2,5-dihydrofuran.

Analysis for C H N O-Calcd.: C, 66.1; H, 3.41; N, 237. Found: C, 66.3; H, 3.37; N, 23.7. This example demonstrates the reaction of tetracyanoethylene oxide with a diacetylenic compound in which unconjugated acetylenic bonds are in relatively close proximity. Thus, reaction with 1,6-hcptadiyne was confined largely to one of the acetylenic bonds when the epoxide to heptadiyne mole ratio was small (i.e., one epoxide group to ca. 6 acetylenic groups). Similarly, reaction will occur at only one acetylenic bond in each of 1,4-pentadiyne and 1,10-dodecadiyne when the latter are substituted for 1,6- heptadiyne in the process of this example.

8 A suspension of 3.0 parts of phenyltricyanoethylene oxide and 2.74 parts of diphenylacetylene in 54 parts of 1, Z-dibromoethane was heated at reflux temperature for 17 hours. The reaction mixture was cooled and concentrated. The residual oil became partially crystalline on standing, and the semisolid was spread on a porous plate to remove liquid impurities. The solid residue (2.61 parts) was recrystallized from ethyl alcohol to give 1.74 parts of pale 1-2 5 S-tricyano-Z 5 -dihy- EXAMPLE X yellow crystals of 2,3 ,4 tripheny l drofuran, MP. 15 15 6 C. The color was removed by further recrystallization. GBH5GEG 0611 (NC)2CO Analysis for C H N OCalcd.: C, 80.4; H, 4.05; N,

0N 11.3. Found: C, 80.6; H, 3.80; N, 11.2.

Additional examples of compounds containing acetyl- O C 6H5 15 enic bonds that will react with polycyanoethylene oxides, (N G) CCN and the corresponding polycyano-2,5-dihydr0furan prod- 6 5 C (35H ucts, are shown in Table I.

Table I Acetylenic Epoxide Reactant Product Reaetant Butyl piolate 0131 210 C G13F27 NCC o-oN Butyl 2,5 dicyano-2,5- di(pe Oyclohexyl fl- (NC)zOC (0N); (NC) C (ONh Oyclohexyl 4-bron 1o-2,2,5,5 bromotetraeyano-Q,5-d1hydro 3- propiolate. BrO C O 05H furoate.

1 O Ethyl 2" (NC)2CC (CN)z (NOMC C (CN)z Ethyl 2,2,5,5-tetraeyano4-(nnonynoate. hexyl)-2,5-d1hydr0-3-furoate..

GH3(CH2)5C C(fiOCgHs Butyl 4- (NO)2C-C (CN): (NChC C (CN)z Butyl 3-(2,2,5,5 tetracyano-2,5- hexy'noate. d1hydro-4-rnethyl-3-fury1)- 0 H 0 (CH2) 2(|3l 0 0 B; l-propanoate.

lMethyl 9- (N C) 2CC (ON) a (NO) 2C C (CN); Methyl 8-[2,2,5,5-tetracyanooctadecynoate. 2,o-d1hydr0-4-(n-octy1)-3- CH3(CH-z) C (GHQ-10 0 CH turyl] 1-0csoate.

l Ii ll Ii Chloroacetylene 0 113(0 E9 10 3 CC C 0 (CH1) 17CH3 011303112) C O C O(CH G H Di-gn-octodecyl) 3-ehloro-2,5-

d1cyano-2,5-d1hydrofuran- CN CN N CC O-CN 2,5-dicarboxy1ate.

II C=' C O1 Propargyl (NCMC 0 (UN): (NCMO O (CNM 3-(Benzoyloxymethyl)-2,2,5,5-

benzoate. tetracyan0-2,5-dihydrofuran.

HGC CHzO (5 C 11 Benzyl propargyl (NO)zC--O (CN)2 (NO)2C 0 (ON); B-(Benzyloxymethyl)-2,2,5,5-

ether. tetraeyano-2,5-dihydroura HC-C CH O CH C H 0 o 9 ll ll I Butynediol CHs(CHz) 30 O O-O Cl CH (CH )3O O O C] n-Butyl 3,4-bis(aeetoxymethyl)- Diacetate. I l 2, ;cyan -2(p-chloropheny)- ON ON C C 2,5-d1hydro-5-iuroate.

N 0 ON OHQFJOCHZC OCHzOfiCHa O O O (C H2)3OTI3 Tetraethyl (NCMC C (CHQgOHa (N C) 2C C-ON 3,4-l 3lS(dietl10Xymethy])-2 5 5. butynedialdetncya-H -n nyl)-2,5-dihyde acetal. ON C2(HsO)2CHC C CBKO C2U5)2 hydrcfuran.

Bis(trifluoromethylthio)acetylene is obtained by reaction of trifiuoromethanesulfenyl chloride and bis(bromomagnesium)acetylide in diethyl ether at 20 to 50 C.

(2,2,3,3-tetrafiuoro-l-cyclobutyl)acetylene can be prepared from tetrafluoroethylene and monovinylacetylene by the procedure described in US. 2,462,345.

Polycyano-Z,S-dihydrofurans are useful as intermediates to corresponding carboxylic acids, salts, esters or amides, obtainable by well known methods of hydrolysis or alcoholysis. For example, sodium 3,4-dirnethyl-2,5- dihydro-2,2,5,5-furantetracarboxylate can be obtained by hydrolysis of 3,4-dirnethyl-2,2,5,5-tetracyano-2,5-dihydrofuran with alcoholic sodium hydroxide; and tetramethyl 2,5-dihydro-2,2,5,5-furantetracarboxylate can be obtained by methanolysis of 2,2,5,S-tetracyano-2,5-dihydrofuran with hydrogen chloride in methanol. Tetracarboxylic acids thus obtained have two malonic acid centers which can each lose carbon dioxide by decarboxylation, and thereby in turn yield corresponding dicarboxylic acids, e.g., 3-phenyl-2,5-dihydrofuran-2,S-dicarboxylic acid from 3-phenyl-2,5-dihydro-2,2,5,S-tetracarboxylic acid obtained by alkaline hydrolysis of 3-phenyl-2,2,5,5-tetracyano-2,5- dihydrofuran. The dicarboxylic acids are obtained directly by acid hydrolysis of the tetracyano compounds, e.g., with hot concentrated aqueous sulfuric acid, since decarboxylation takes place concurrently with hydrolysis under such conditions. These various polyfunctional carboxylic acids, esters and amides are useful further in the preparation of condensation polymers such as polyamides by reaction under dehydrating conditions of the free acids with diamines, e.g., hexamethylene diamine, or polyesters by polyesterification of the acids or ester interchange of the esters with glycols, e.g., ethylene glycol. Such polyamides and polyesters are plastic materials which can be used in the form of fibers, self-supporting films or molded objects. For example, the polyester of ethylene glycol and 2,5-dihydro-2,5-furandicarboxylic acid (obtainable by acid hydrolysis of the product of Example I) is useful in the form of self-supporting films and fibers.

Since obvious modifications and equivalents in the invention will be apparent to those skilled in the chemical arts, I propose to be bound solely by the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula E wherein A is a member selected from the group consisting of hydrogen, cyano, R, C(O)OR, polyfluoro R and phenylene X, R being alkyl of 1-18 carbons and X being in the para position and a member selected from the group consisting of hydrogen, halogen, nitro, R and OR; B is a member selected from the group consisting of cyano, C(O)OR and polyfluoro R; D contains up to 12 carbons and is a member selected from the group consisting of hydrogen, R, halo R 14 in which all halogens are of atomic number 9-35, CH OR, C(O)OR", CH OC(O)R", alkylene- C(O)OR", dialkoxymethyl and polyfluoroalkylthio, R being a member selected from the group consisting of alkyl, aryl, cycloalkyl, alkynyl, aralkyl, alkaryl, arcycloalkyl, cycloalkylaryl, alkcycloalkyl, cycloalkylalkyl, and aralkynyl and R" being a member selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, alkaryl, arcycloalkyl, cycloalkylaryl, alkcycloalkyl, and cycloakylalkyl; and

E is a member selected from the group consisting of D,

halogen of atomic number 17-35, cyano and QUIPMN with an acetylenic compound of the formula D CEC-E' at a temperature of at least C.,

A, B and D being as defined in claim 1, and

E being a member selected from the group consisting of D, halogen of atomic number 17-35 and cyano.

8. The process of claim 7 where all carbon-carbon double bonds in the acetylenic reactant are conjugated with a carbon-carbon triple bond.

9. The process of claim 7 where the mole ratio of polycyanoethylene oxide to reactive carbon-carbon triple bond in the acetylenic compound is about 1:1.

10. The process of claim 7 where the reaction is conducted at a temperature of C.-250 C., and a compound of claim 1 is separated from the resultant product mixture.

References Cited by the Examiner UNITED STATES PATENTS 3,024,278 3/ 1962 Groenweghe 260-346.1 X

NICHOLAS S. RIZZO, Primary Examiner. JOHN D. RANDOLPH, Examiner. 

1. A COMPOUND OF THE FORMULA 